JP2003514767A - Keratin fiber dye preparation - Google Patents

Abstract

A coloring composition and a method of coloring keratin-containing fibers are provided. The coloring composition contains a mixture of and/or a reaction product of at least one aromatic aldehyde or ketone and at least one CH-active compound. In the method of the present invention, the aromatic aldehyde or ketone and the CH-active compound may be applied to keratin-containing fibers simultaneously or successively.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to a composition containing a combination of an aromatic aldehyde or ketone and a CH-active compound for dyeing keratin fibers (particularly human hair), dyeing in a hair dyeing composition. It relates to the use of said combination as an ingredient, as well as a method of dyeing keratin-containing fibers, especially human hair.

BACKGROUND ART Keratin-containing fibers, such as hair, wool or fur, are usually dyed with direct or oxidative dyes. The oxidative dye is one or more first intermediates (E
ntwicklerkomponenten) or the first intermediate and one or more second intermediates (Kupplerkomponenten) are formed by oxidative coupling. The first and second intermediates are also known as oxidative dye precursors.

Commonly used first intermediates are primary aromatic amines, diaminopyridine derivatives, which additionally have a free or substituted hydroxy or amino group in the para or ortho position.
Heterocyclic hydrazones, 4-aminopyrazolone derivatives, and 2,4,5,6-tetraaminopyrimidine and its derivatives.

Examples thereof include p-phenylenediamine, p-toluylenediamine, 2,4,5,6-
Tetraaminopyrimidine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) -Ethanol, 1-phenyl-3-carboxamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-
Aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4
-Dihydroxy-5,6-diaminopyrimidine, and 2,5,6-triamino-
It is 4-hydroxypyrimidine.

The second intermediates are typically m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols, and substituted pyridine derivatives. Particularly suitable second intermediates are α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-
Methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmanns
Blue), 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-
Aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 2
-Chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 3-amino-6-methoxy-2-methylaminopyridine, and 3,5 -Diamino-2,6-dimethoxypyridine.

For other conventional dye components, see also in particular: “Dermatology”
Series (edited by Ch. Culnan and H. Maibach), Marcel Dekker Inc. ,
New York / Basel, 1986, Volume 7, Ch. Zviak, The Science of
Hair Care, Chapter 7 (pp. 248-250; direct dyes) and Chapter 8 (26)
4-267; oxidative dye precursors), and "Europaeische Inventar der K"
osmetik-Rohstoffe "(published by European Commission, Bundesverband Deutscher Industrie- und Handelsunternehmen in floppy disk form.
fuer Arzneimittel, Reformwaren und Koerperpflegemittel e.V. , Mannheim, Germany).

Oxidative dyes give high-purity colors with good durability, but the development of such colors is usually carried out under the action of an oxidizing agent (eg H ₂ O ₂ ) Oxidizing agents can damage fibers. Moreover, certain oxidative dye precursors or mixtures of oxidative dye precursors are often irritating to sensitive persons with skin.
Direct dyes are applied under milder conditions, but have the disadvantage that the resulting color is often not sufficiently durable.

DISCLOSURE OF THE INVENTION The use of a combination of aromatic aldehydes or ketones and CH-active compounds for dyeing keratin-containing fibers is described below, but this is not known to date.

An object of the present invention is to provide a dye for keratin fibers (particularly human hair), which has performance comparable to conventional oxidative hair dyes in terms of color strength, gray hiding and durability. However, the oxidant (eg, H ₂ O ₂ ) was to provide a dye that does not necessarily have to be included. Furthermore, the dyes of the present invention, if irritating, have very low levels.

Surprisingly, an aromatic aldehyde or ketone of formula (I)
II) and / or a combination with a CH-active compound of formula (III),
It was found to be very suitable for dyeing keratin-containing fibers even in the absence of oxidizing agents. Such compounds give very vivid and deep colors and lead to a wide range of shades. However, in principle, an oxidizing agent may be present.

The present invention relates to a keratin-containing fiber (especially human hair) dyeing composition, which comprises an aromatic aldehyde or ketone of formula I and a formula II and / or a formula II
In combination with a CH-active compound of formula I and / or a reaction product of a compound of formula I with formula II and / or formula III:

[0012]   Formula I:

[Chemical 10] [In the formula, R ¹ is a hydrogen atom, a C _1-4 alkyl group or an aryl group, and R ² and R ³ are independently of each other a hydrogen atom, a C _1-4 alkyl group, a halogen atom, hydroxy, C _{1 -4} alkoxy or nitro group or together form a fused aromatic ring, R ⁴ and R ⁵ are hydrogen atom, C _1-4 alkyl, C _2-4 hydroxyalkyl, C _1-4 alkenyl or aryl. 5, 6 or 7 which are saturated or unsaturated in combination with one of the substituents R ² or R ³ to form a 5- to 7-membered heterocycle, which is either a group or in combination with a nitrogen atom. form a-membered ring, Q is a direct bond or a vinylene or vinylidene group, which is two one jointly with the indole ring or substituents R ⁴ or R ⁵ (when forming the exocyclic double bond) It can form Ndorin ring, n is 1 or 2. ];

[0013]   Formula II:

[Chemical 11] [Wherein, R ⁶ is C _1-10 alkyl, C _2-10 alkenyl, C _2-4 hydroxyalkyl, C _2-4 carboxyalkyl, C _2-4 sulfoalkyl or aralkyl group, and R ⁷ and R ⁸ Are independently a hydrogen atom, a C _1-4 alkyl group, a halogen atom, hydroxy, a C _1-4 alkoxy or nitro group, or jointly form a condensed aromatic ring, and R ⁹ is a hydrogen atom, C _{1-4 is} an alkyl or aryl group, X is an oxygen or sulfur atom, the group> N—R ¹² or —CH═CH—, where R ¹² is C _1-4 alkyl, C _2-4 carboxyalkyl, C _{2-4 sulfoalkyl, C 2-4} sulfoxide _{alkyl, C 2-4} hydroxyalkyl or aralkyl group, Y ^- is _{halide, C 1-4} alkylsulfamoyl Eto, C _1-4 alkane sulfonates, a anion selected arenesulfonate, C _1-4 perfluoroalkane sulfonate, tetrafluoroborate, par halogenoalkyl sulfonates, sulfates, hydrogen sulfates or carbonates. ];

[0014]   Formula III:

[Chemical 12] [In the formula,   R¹⁰Is C_1-4Acyl group, aroyl, C_1-4Alkylsulfonyl, C_{1- Four} Alkylsulfinyl, C_1-4Alkylamino, di-C_1-4-Alkyla
Mino, vinyl carbonyl, methine imino, nitrile, ester or carboxylic acid
Amido group (optionally C_1-4Alkyl, C_2-4Hydroxyalkyl or
Optionally substituted with an aryl group),   R¹¹Is C_1-4Acyl, C_1-4Alkoxy, C_1-4Alkylamino, C _1-4 Acylamino or di-C_1-4An alkylamino group,   Substituent R¹⁰And R¹¹In cooperation with the rest of the molecule, 1,3-thiazolidine
-2,5-diones, 1,3-thiazolidine-2-thione-5-ones, perch
Doropyrimidine-2,4,6-triones, perhydropyrimidine-2-thione
-4,6-diones, cyclopentane-1,3-diones, cyclohexane-1
, 3-diones, indolines, indane-1,3-diones, indane-1-
Ones, 2-pyrazolin-5-ones, 1,2-dihydro-6-hydroxy-2
Selected from the series of hydroxypyridines or their enol esters
Forming a 5-, 6- or 7-membered heterocycle,   Z is an oxygen, sulfur or dicyanomethylene group. ].

In the present invention, keratin-containing fibers are understood to include wool, fur, feathers and especially human hair. Basically, however, the dyes of the present invention are not limited to other natural fibers (eg cotton, jute, sisal, linen or silk), modified natural fibers (eg regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetal cellulose), and synthetic fibers. It may also be used for dyeing fibers such as polyamide, polyacrylonitrile, polyurethane and polyester fibers.

Preferred compounds of formula I are exemplified below: 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 4-pi Peridinobenzaldehyde, 4-dimethylaminoacetophenone, 4-dimethylaminonaphthalaldehyde, 4-dimethylaminobenzylideneacetone, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethyl Amino-2-methylbenzaldehyde, trans-4-diethylaminocinnamaldehyde, 4- (dibutylamino) -benzaldehyde, 4-diphenylaminobe Insaldehyde, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 2,3,6,7-tetrahydro-8. -Hydroxy-1H
, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 4- (1-imidazolyl) -benzaldehyde, 2-morpholinobenzaldehyde, indole-3-carboxaldehyde, 1-methylindole-3-carboxaldehyde,
N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3
Trimethylindoline (Fischer aldehyde or tribasic aldehyde) and mixtures thereof.

Preferred compounds of formula II are exemplified below: 1,4-dimethylquinolinium, 1,2-dimethylquinolinium, 1,4-dimethylpyridinium, 1,2-
Dimethylpyridinium, 2-methyl-1-ethylquinolinium, 2,3-dimethylisoquinolinium, 1,2,3,3-tetramethyl-3H-indolinium,
2,3-Dimethylbenzothiazolium, 2,3-dimethyl-6-nitrobenzothiazolium, 3-benzyl-2-benzothiazolium, 2-methyl-3-propylbenzothiazolium, 2,4 -Dimethyl-3-ethylthiazolium, 3- (2
-Carboxyethyl) -2,5-dimethylbenzothiazolium, 1,2,3-trimethylbenzimidazolium, 5,6-dichloro-1,3-diethyl-2-methylbenzimidazolium, 3-ethyl-2 -Methylbenzothiazolium, 3-
Ethyl-2-methylnaphthol [1,2-d] thiazolium, 5-chloro-3-
Ethyl-2-methylbenzothiazolium, 3-ethyl-2-methylbenzoxazolium salt (for example, chloride, bromide, iodide, methanesulfonate, benzenesulfonate, p-toluenesulfonate, trifluoromethanesulfonate, methylsulfate) , Tetrafluoroborate), and 2-methyl-3- (3-sulfopropyl) -benzothiazolium hydroxide, inner salt, 5-methoxy-2-methyl-3- (3-sulfopropyl). ) -Benzothiazolium hydroxide, inner salts, and mixtures thereof.

Examples of compounds of formula III are: Rhodanine, Rhodanine-3-acetic acid, Barbituric acid, Thiobarbituric acid, 1,3-Dimethyl and 1,3-diethylthiobarbituric acid, Oxindole, 3-indoxyl acetate, coumaranone, 1-methyl-3-phenylpyrazolinone, indan-1,3-dione,
Cyclopentane-1,3-dione, 1,2-dihydro-1-ethyl-6-hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile and mixtures thereof.

Illustrative reaction products of compounds of Formula I and Formula II and / or Formula III are: Quinaldine Red (2- [4- (dimethylamino) -styryl] -1-ethylquinolinium iodide ), 2- [4- (dimethylamino) -styryl] -1-
Methylquinolinium iodide, 2- [4- (dimethylamino) -styryl]-
1-ethylpyridinium iodide, 2- [4- (dimethylamino) -styryl] -1-methylpyridinium iodide, 4- [4-dimethylaminostyryl]
-1-Methylpyridinium tosylate, 4- [2- (2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolidin-9-yl) -ethenyl] -1-
Methylpyridinium iodide, trans-4- [4- (dibutylamino) -styryl] -1-methylpyridinium iodide and 2,6-bis- [4- (dimethylamino) -styryl] -1-methylpyridinium iodide , 2- [4-
(Dimethylamino) -styryl] -3-methylbenzoxazolium perchlorate, 2- [4- (dimethylamino) -styryl] -3-methylbenzoxazolium iodide, 2- [4- (dimethylamino) -Styryl-1-ethylnaphthol [1,2-d] thiazolium iodide. Many of the compounds as described above are known from the literature or are commercially available or can be obtained by known synthetic methods.

The compounds represented by the above formulas I, II and III are preferably contained in the composition of the present invention in an amount of 0.03 to 65 mmol, more preferably 1 to 40 mmol, per 100 g of the total dye composition. Use in quantity. The compounds can be used as direct dyes or in the presence of conventional oxidative dye precursors.

Dye compositions containing only the combination according to the invention as dyeing constituents are preferably used for dyeing in the yellow, orange, red and violet regions. To obtain other colors and purer colors, the dye compositions of the present invention may further contain color improvers. Color improvers include piperidine, piperidine-2-carboxylic acid,
Piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5- Carboxylic acid, pyrazole, 1,2,4-triazole,
It is preferably selected from the group consisting of piperazine, their derivatives and physiologically compatible salts.

The color improver is 0.03 to 65 mmol per 100 g of the entire dye composition,
In particular, it can be used in an amount of 1 to 40 mmol. Various combinations of compounds of formula I, II and / or III may be used in combination in any dye composition. Similarly, various color improvers may be used in combination.

No oxidizing agent (eg H ₂ O ₂ ) need be present. However, in some cases it may be desirable to add hydrogen peroxide or other oxidizing agents to the compositions of the present invention in order to obtain a lighter color than the keratin-containing fibers to be dyed. The oxidizing agent is usually used in an amount of 0.01 to 6% by weight, based on the applied solution. A preferred oxidizing agent for human hair is H ₂ O ₂ .

In a preferred embodiment, the dye composition of the present invention further contains a conventional direct dye, in addition to the compound used according to the present invention, in order to further adjust the color tone. Direct dyes are selected, for example, from nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols. Examples of suitable direct dyes are the compounds known under the following international or trade names: HC Yellow 2, HC Yellow
w 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC
Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue
e 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Dispers
e Violet 4, Disperse Black 9, Basic Brown 16, and Basic Bro
wn 17, as well as picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphenylamine-2′-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis- (
2'-Hydroxyethylamino) -2-nitrobenzene hydrochloride, and 1-methyl-3-nitro-4- (2'-hydroxyethyl) -aminobenzene. The composition of this aspect of the present invention comprises a direct dye, preferably 0.
It is contained in an amount of 01 to 20% by weight.

The composition of the present invention further comprises naturally occurring dyes such as henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, ilex bark, sage, reed tree, rape root, catechu. , Sedre and Arcanet may be included.

The compounds I and II used according to the invention, or optionally the color improvers and direct dyes, need not be a single compound. The hair dyeing composition of the present invention requires the elimination of small amounts of other components due to the method of making each dye, either because it adversely affects the dyeing result or for other reasons (e.g. toxicological reasons). It may be included unless otherwise specified. The dyes of the invention produce highly pure colors even at physiologically acceptable temperatures below 45 ° C. Therefore, the dye of the present invention is particularly suitable for dyeing human hair. For application to human hair, dyes are usually combined in water-containing cosmetic carriers. Suitable water-containing cosmetic carriers are, for example, creams, emulsions, gels or effervescent solutions containing surfactants (eg shampoos) or other formulations suitable for application to keratin-containing fibers. The dye may be combined in a water-free carrier.

The dye composition of the present invention may also contain known active substances, additives and auxiliaries which are usually present in such formulations. Dye compositions often contain at least one surfactant. In principle, anionic, zwitterionic, amphoteric, nonionic and cationic surfactants are all suitable. However, in many cases it has proved advantageous to select from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants for the compositions according to the invention are anionic surfactants suitable for use on the human body. Such materials have water-solubilizing anionic groups, such as carboxylate, sulfate, sulfonate or phosphate groups, and lipophilic alkyl groups of about 10-22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether, amide and hydroxyl groups also
It can be present in the molecule. Sodium, potassium and ammonium salts and mono-
Examples of suitable anionic surfactants in the form of diammonium, di- and trialkanol ammonium salts (alkanol groups containing 2 or 3 carbon atoms) are given below:

[0029] - straight chain fatty acid having a carbon number of 10 to 22 (soaps), - _{formula: R-O- (CH 2 -CH} 2 O) x -CH 2 -COOH [ wherein, R 10 carbons
22 straight-chain alkyl groups, and x = 0 or 1-16. ] An ether carboxylic acid represented by: an acyl group having 10 to 18 carbon atoms, an acyl sarcoside, an acyl group having 10 to 18 carbon atoms, an acyl taurate, an acyl group having 10 to 18 carbon atoms, an alkyl group A C8-18 sulfosuccinic acid mono- and dialkyl ester, and an alkyl group C8-18 / oxyethyl group C1-6 sulfosuccinic acid monoalkyl polyoxyethyl ester, a C12-18 straight chain alkane sulfonates, linear α- olefin sulfonates, of-carbon atoms from 12 to 18 fatty α- sulfo fatty acid methyl ester-12 to 18 carbon atoms, - _{formula: R-O- (CH 2 -CH} 2 O) x -SO ₃ H [In the formula, R is preferably a linear alkyl group having 10 to 18 carbon atoms, and x = 0 or 1 to 12. ] A mixture of surface-active hydroxy sulfonate according to DE-A-372530, a sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-3723354, Sulfonate of unsaturated fatty acid having 12 to 24 carbon atoms / 1 to 6 double bonds according to DE-A-3926344, and about 2 to 15 molecules of ethylene oxide and / or propylene oxide added to fatty alcohol having 8 to 22 carbon atoms. Esters of tartaric acid and citric acid with alcohols in the product form.

Preferred anionic surfactants are alkyl sulphates, alkyl polyglycol ether sulphates and ether carboxylic acids (where the alkyl group has 1 carbon atom).
0-18, up to 12 glycol ether groups in the molecule), and especially salts of saturated and especially unsaturated C _8-22 carboxylic acids (eg oleic acid, stearic acid, isostearic acid and palmitic acid).

In the present invention, a zwitterionic surfactant is a surface-active compound having at least one quaternary ammonium group and at least one —COO ⁻ or —SO ₃ ^— group in the molecule. Particularly suitable zwitterionic surfactants are so-called betaines such as N-alkyl-N, N-dimethylammonium glycinate (eg coconut oil alkyldimethylammonium glycinate), N-acylaminopropyl-N, N-dimethyl. Ammonium glycinate (for example, coconut oil acylaminopropyldimethylammonium glycinate), and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazoline having an alkyl or acyl group having 8 to 18 carbon atoms, and palm. Oil acylaminoethyl hydroxyethyl carboxymethyl glycinate. Preferred zwitterionic surfactants are CT
FA is a fatty acid amide derivative known as Cocamidopropyl Betaine.

Amphoteric surfactants have at least one free amino group and at least one —COOH or —SO ₃ H group in the molecule in addition to a C _8-18 alkyl or acyl group, It is a surface-active compound capable of forming a salt. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyl. Taurine, N-alkyl sarcosine,
2-Alkylaminopropionic acid and alkylaminoacetic acid (wherein the alkyl group has about 8 to 18 carbon atoms). Particularly preferred amphoteric surfactants are N-coconut oil alkylaminopropionate, coconut oil acylaminoethylaminopropionate,
And C _12-18 acyl sarcosine.

The nonionic surfactant has, for example, a polyol group, a polyalkylene glycol ether group, or a polyol / polyglycol ether group combination as a hydrophilic group. Examples of such compounds are: -Ethylene oxide 2-3 of a straight chain fatty alcohol having 8 to 22 carbon atoms, a fatty acid having 12 to 22 carbon atoms, and an alkylphenol having 8 to 15 carbon atoms in the alkyl group.
0 mol and / or 0 to 5 mol propylene oxide adduct, 1 to 30 mol adduct of glycerol with ethylene oxide, C _12-22 fatty acid monoesters and diesters, C _8-22 alkyl mono- and oligoglycosides and their Ethoxylated analogues: 5-60 mol ethylene oxide adducts of castor oil and hydrogenated castor oil, ethylene oxide adducts of sorbitan fatty acid esters, ethylene oxide adducts of fatty acid alkanolamides.

Examples of suitable cationic surfactants for use in the hair treatment formulations of the present invention are:
Among others, quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides such as: alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and trialkylmethylammonium chloride such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride. , Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Other suitable cationic surfactants for use in accordance with the present invention are quaternized protein hydrolysates.

The following exemplary cationic silicone oils are also suitable for use in accordance with the present invention: Commercially available Q2-7224 (Manufacturer: Dow Corning; Stabilized Trimethylsilyl Amodimethicone), Dow Corning. 929 Emulsion (A
Contains a hydroxyamino-modified silicone, also known as modimethicone), S
M-2059 (Manufacturer: General Electric), SLM-55067 (Manufacturer:
Wacker), and Abil (TM) -Quat 3270 and 3272 (manufacturer: Th.
Goldschmidt; diquaternary polydimethylsiloxane, Quaternium-80).

Alkylamido amines, especially fatty acid amido amines such as Tego Amid (
Stearylamidopropyldimethylamine, available under the trademark S18, exhibits a favorable conditioning effect and is especially readily biodegradable. Quaternary ester compounds, so-called "esterquats", such as methyl hydroxyalkyl dialcoyloxyalkyl ammonium methosulfate [commercially available under the trade name of Stepantex (TM)], are also readily biodegradable.

One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat ™ 100 (CTFA name: Lauryl Methyl Gluceth).
-10 Hydroxypropyl Dimonium Chloride). The compound having an alkyl group used as a surfactant may be a single compound. However, since such compounds are usually produced from natural plant or animal raw materials, they are obtained as a mixture of compounds having different alkyl chain lengths depending on the raw materials.

Surfactants which are ethylene oxide and / or propylene oxide adducts of fatty alcohols, or derivatives of such adducts, have products with a “normal” homolog distribution, and products with a narrow homolog distribution. It may be any one.
A product with a "normal" homolog distribution is a homolog mixture obtained by reaction of a fatty alcohol with an alkylene oxide, using an alkali metal, alkali metal hydroxide or alkali metal alcoholate as catalyst. On the other hand, a narrow homolog distribution is obtained when, for example, hydrotalcites, alkaline earth metal salts of ethercarboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. It may be advantageous to use products with a narrow homolog distribution.

Other active substances, auxiliaries and additives are exemplified as follows: Nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers, and polysiloxanes, cations Polymers, such as quaternized cellulose ethers, quaternary group-containing polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide / dimethyldiallylammonium chloride copolymers, dimethylaminoethylmethacrylate / vinylpyrrolidone copolymers quaternized with diethylsulfate. , Vinylpyrrolidone / imidazolinium metochloride copolymers, and quaternized polyvinyl alcohols, zwitterionic and amphoteric polymers such as acryl Amidopropyl - trimethylammonium chloride / acrylate copolymers, and octylacrylamide / methyl methacrylate / t-butyl aminoethyl methacrylate / 2-
Hydroxypropyl methacrylate copolymers, Anionic polymers such as polyacrylic acid, crosslinked polyacrylic acid, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / Maleic anhydride copolymer, and acrylic acid / ethyl acrylate / Nt-butyl acrylamide terpolymer,

Thickeners such as agar, guar gum, alginates, xanthan gum, gum arabic, indian gum, carob flour, linseed gum, dextran, cellulose derivatives (eg methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose), starch fractions and derivatives (eg amylose). ,
Amylopectin and dextrin), clay (eg bentonite), or pure synthetic hydrocolloids (eg polyvinyl alcohol), structuring agents such as glucose and maleic acid, hair conditioning compounds such as phospholipids (such as soy lecithin, egg lecithin and kephalin) ), And silicone oils, protein hydrolysates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, condensation products of these with fatty acids, and quaternized protein hydrolysates,

Perfume oils, dimethylisosorbide and cyclodextrins, solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, antidandruff agents such as Piroctone Olamine and Zinc Omadine, for pH value adjustment Other substances, active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acid and its salts, plant extracts and vitamins, cholesterol, UV filters,

Consistency factors such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, fatty acid alkanolamides, complexing agents , EDTA, NTA and phosphonic acids, swelling and penetrating agents, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas, primary, secondary and tertiary phosphates, imidazoles, tannins. , An emulsifier, eg a latex, a pearlescent agent, eg ethylene glycol mono- and distearate, a propellant, eg a propane / butane mixture, N ₂ O, dimethyl ether, CO ₂ and Air, and-Antioxidants.

To prepare the dye composition of the present invention, the components of the water-containing carrier are used in the amounts customary for that purpose. For example, an emulsifier of 0.5 to 30 is added to the whole dye composition
It is used in a concentration of wt.% And the thickener is used in a concentration of 0.1-25% by weight.

The addition of ammonium or metal salts to the dye composition can be advantageous for the dyeing result. Examples of suitable metal salts are alkali metal (eg potassium, sodium or lithium), alkaline earth metal (eg magnesium, calcium, strontium or barium), or aluminum, manganese, iron, cobalt, copper or zinc formate. , Carbonate, halide, sulfate, butyrate, valerate, capronate, acetate, lactate, glycolate, tartrate, citrate, gluconate, propionate, phosphate and It is a phosphonate. Preferred are sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, ammonium chloride and ammonium acetate. Such salt is 100 g of the entire dye composition.
It is preferably present in an amount of 0.03 to 65 mmol, more preferably 1 to 40 mmol. The pH value of the ready-to-use dyeing composition is usually in the range of 2 to 12, preferably 4 to 10.

The present invention provides the oxidative dyeing of a combination of an aromatic aldehyde or ketone of formula I with a CH-active compound of formula II and / or formula III and / or the reaction product of said compound. It also relates to its use as a dyeing component in hair compositions:

[0046]   Formula I:

[Chemical 13] [In the formula, R ¹ is a hydrogen atom, a C _1-4 alkyl group or an aryl group, and R ² and R ³ are independently of each other a hydrogen atom, a C _1-4 alkyl group, a halogen atom, hydroxy, C _{1 -4} alkoxy or nitro group or together form a fused aromatic ring, R ⁴ and R ⁵ are hydrogen atom, C _1-4 alkyl, C _2-4 hydroxyalkyl, C _1-4 alkenyl or aryl. 5, 6 or 7 which are saturated or unsaturated in combination with one of the substituents R ² or R ³ to form a 5- to 7-membered heterocycle, which is either a group or in combination with a nitrogen atom. form a-membered ring, Q is a direct bond or a vinylene or vinylidene group, which is two one jointly with the indole ring or substituents R ⁴ or R ⁵ (when forming the exocyclic double bond) It can form Ndorin ring, n is 1 or 2. ];

[0047]   Formula II:

[Chemical 14] [Wherein, R ⁶ is C _1-10 alkyl, C _2-10 alkenyl, C _2-4 hydroxyalkyl, C _2-4 carboxyalkyl, C _2-4 sulfoalkyl or aralkyl group, and R ⁷ and R ⁸ Are independently a hydrogen atom, a C _1-4 alkyl group, a halogen atom, hydroxy, a C _1-4 alkoxy or nitro group, or jointly form a condensed aromatic ring, and R ⁹ is a hydrogen atom, C _{1-4 is} an alkyl or aryl group, X is an oxygen or sulfur atom, the group> N—R ¹² or —CH═CH—, where R ¹² is C _1-4 alkyl, C _2-4 carboxyalkyl, C _{2-4 sulfoalkyl, C 2-4} sulfoxide _{alkyl, C 2-4} hydroxyalkyl or aralkyl group, Y ^- is _{halide, C 1-4} alkylsulfamoyl Eto, C _1-4 alkane sulfonates, a anion selected arenesulfonate, C _1-4 perfluoroalkane sulfonate, tetrafluoroborate, par halogenoalkyl sulfonates, sulfates, hydrogen sulfates or carbonates. ];

[0048]   Formula III:

[Chemical 15] [In the formula,   R¹⁰Is C_1-4Acyl group, aroyl, C_1-4Alkylsulfonyl, C_{1- Four} Alkylsulfinyl, C_1-4Alkylamino, di-C_1-4-Alkyla
Mino, vinyl carbonyl, methine imino, nitrile, ester or carboxylic acid
Amido group (optionally C_1-4Alkyl, C_2-4Hydroxyalkyl or
Optionally substituted with an aryl group),   R¹¹Is C_1-4Acyl, C_1-4Alkoxy, C_1-4Alkylamino, C _1-4 Acylamino or di-C_1-4An alkylamino group,   Substituent R¹⁰And R¹¹In cooperation with the rest of the molecule, 1,3-thiazolidine
-2,5-diones, 1,3-thiazolidine-2-thione-5-ones, perch
Doropyrimidine-2,4,6-triones, perhydropyrimidine-2-thione
-4,6-diones, cyclopentane-1,3-diones, cyclohexane-1
, 3-diones, indolines, indane-1,3-diones, indane-1-
Ones, 2-pyrazolin-5-ones, 1,2-dihydro-6-hydroxy-2
Selected from the series of hydroxypyridines or their enol esters
Forming a 5-, 6- or 7-membered heterocycle,   Z is an oxygen, sulfur or dicyanomethylene group. ].

The present invention is a method for dyeing keratin-containing fibers (especially human hair), comprising an aromatic aldehyde or ketone of formula I and a CH-active compound of formula II and / or formula III. And / or reaction products of the above compounds,
And a method comprising applying a dye composition containing conventional cosmetic ingredients to a keratin-containing fiber, leaving it for a period of time (typically about 30 minutes) and then rinsing or shampooing:

[0050]   Formula I:

[Chemical 16] [In the formula, R ¹ is a hydrogen atom, a C _1-4 alkyl group or an aryl group, and R ² and R ³ are independently of each other a hydrogen atom, a C _1-4 alkyl group, a halogen atom, hydroxy, C _{1 -4} alkoxy or nitro group or together form a fused aromatic ring, R ⁴ and R ⁵ are hydrogen atom, C _1-4 alkyl, C _2-4 hydroxyalkyl, C _1-4 alkenyl or aryl. 5, 6 or 7 which are saturated or unsaturated in combination with one of the substituents R ² or R ³ to form a 5- to 7-membered heterocycle, which is either a group or in combination with a nitrogen atom. form a-membered ring, Q is a direct bond or a vinylene or vinylidene group, which is two one jointly with the indole ring or substituents R ⁴ or R ⁵ (when forming the exocyclic double bond) It can form Ndorin ring, n is 1 or 2. ];

[0051]   Formula II:

[Chemical 17] [Wherein, R ⁶ is C _1-10 alkyl, C _2-10 alkenyl, C _2-4 hydroxyalkyl, C _2-4 carboxyalkyl, C _2-4 sulfoalkyl or aralkyl group, and R ⁷ and R ⁸ Are independently a hydrogen atom, a C _1-4 alkyl group, a halogen atom, hydroxy, a C _1-4 alkoxy or nitro group, or jointly form a condensed aromatic ring, and R ⁹ is a hydrogen atom, C _{1-4 is} an alkyl or aryl group, X is an oxygen or sulfur atom, the group> N—R ¹² or —CH═CH—, where R ¹² is C _1-4 alkyl, C _2-4 carboxyalkyl, C _{2-4 sulfoalkyl, C 2-4} sulfoxide _{alkyl, C 2-4} hydroxyalkyl or aralkyl group, Y ^- is _{halide, C 1-4} alkylsulfamoyl Eto, C _1-4 alkane sulfonates, a anion selected arenesulfonate, C _1-4 perfluoroalkane sulfonate, tetrafluoroborate, par halogenoalkyl sulfonates, sulfates, hydrogen sulfates or carbonates. ];

[0052]   Formula III:

[Chemical 18] [In the formula,   R¹⁰Is C_1-4Acyl group, aroyl, C_1-4Alkylsulfonyl, C_{1- Four} Alkylsulfinyl, C_1-4Alkylamino, di-C_1-4-Alkyla
Mino, vinyl carbonyl, methine imino, nitrile, ester or carboxylic acid
Amido group (optionally C_1-4Alkyl, C_2-4Hydroxyalkyl or
Optionally substituted with an aryl group),   R¹¹Is C_1-4Acyl, C_1-4Alkoxy, C_1-4Alkylamino, C _1-4 Acylamino or di-C_1-4An alkylamino group,   Substituent R¹⁰And R¹¹In cooperation with the rest of the molecule, 1,3-thiazolidine
-2,5-diones, 1,3-thiazolidine-2-thione-5-ones, perch
Doropyrimidine-2,4,6-triones, perhydropyrimidine-2-thione
-4,6-diones, cyclopentane-1,3-diones, cyclohexane-1
, 3-diones, indolines, indane-1,3-diones, indane-1-
Ones, 2-pyrazolin-5-ones, 1,2-dihydro-6-hydroxy-2
Selected from the series of hydroxypyridines or their enol esters
Forming a 5-, 6- or 7-membered heterocycle,   Z is an oxygen, sulfur or dicyanomethylene group. ].

An aromatic aldehyde or ketone of formula I and a formula II and / or formula III
The CH-active compound represented by may be applied to hair at the same time or sequentially. In the latter case, either of the two components may be applied first. The ammonium or metal salt optionally used may be added to either the first component or the second component. There may be up to 30 minutes between application of the first component and application of the second component. The fibers may be pretreated with a salt solution.

An aromatic aldehyde or ketone of formula I and a formula II and / or formula III
May be stored separately or together, and may be stored as a liquid or pasty formulation (aqueous or water free) or as a dry powder. If the components are stored separately, mix well just prior to application. For dry storage, a quantity of warm water (30-80 ° C) is usually added prior to application to prepare a homogeneous mixture.

[0055] The practice of preparing water in 25ml examples staining solution, suspension and aromatic aldehyde or ketone 5 mmol of formula I, a suspension of CH- active compound 5 mmol of formula II or formula III Was prepared at 60 ° C. After cooling to 30 ° C., the suspensions were combined, 5 mmol sodium acetate, optionally 5 mmol piperidine, and 1 drop 20% fatty alkyl ether sulphate solution were added and the pH was adjusted with dilute NaOH or hydrochloric acid. When using the reaction product of the compound of formula I with the compound of formula II or formula III, 5 mmol of the reaction product was suspended or dissolved in 50 ml of water.

Non-pretreated 90% gray human hair tresses were placed in the dyeing solution at 30 ° C. for 30 minutes. The human hair tresses were then rinsed with warm water for 30 seconds, dried with warm air and then combed. The colors and color strengths are shown in the following table. The color intensity was evaluated according to the following criteria:-: very light even if there is color (+): low purity +: medium purity + (+): medium to high purity ++: high purity ++ (+): High to very high purity +++: Very high purity

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Doris Oberkobush             Federal Republic of Germany Day-40591 Düssel             Dolph, Auhum Lot 81 (72) Inventor Horst Hefkes             Federal Republic of Germany Day-40595 Düssel             Dolph, Carlo-Schmidt-Streller             # 113 F-term (reference) 4C083 AC551 AC552 AC851 AC852                       AC861 AC862 CC36 DD27                       EE26                 4H057 AA02 BA01 BA09 CA07 CB45                       CB46 DA01 DA21

Claims (13)

[Claims] 1. A composition for dyeing keratin-containing fibers, especially human hair.
An aromatic aldehyde or ketone of formula I as a dyeing component
In combination with a CH-active compound of formula II and / or formula III, and
And / or a composition containing the reaction product of the above compound:   Formula I: [Chemical 1] [In the formula, R¹Is a hydrogen atom, C_1-4An alkyl group or an aryl group,   R^TwoAnd R^ThreeAre independently of each other a hydrogen atom, C_1-4Alkyl group, halogen source
Child, hydroxy, C_1-4An alkoxy or nitro group or jointly
Forming a condensed aromatic ring,   R^FourAnd R⁵Is a hydrogen atom, C_1-4Alkyl, C_2-4Hydroxy alk
Le, C_1-4An alkenyl or aryl group, or in combination with a nitrogen atom
, A 5- to 7-membered heterocycle, or one of them is a substituent R^TwoOr R^Three Forming a saturated or unsaturated 5-, 6- or 7-membered ring with one of   Q is a direct bond or a vinylene or vinylidene group, which has two substitutions
Group R^FourOr R⁵Forms an indole ring or (an exocyclic double bond with one of the
In some cases) may form an indoline ring,   n is 1 or 2. ];   Formula II: [Chemical 2] [In the formula,   R⁶Is C_1-10Alkyl, C_2-10Alkenyl, C_2-4Hydroxyal
Kill, C_2-4Carboxyalkyl, C_2-4Sulfoalkyl or aralkyl
The base,   R⁷And R⁸Are independently of each other a hydrogen atom, C_1-4Alkyl group, halogen
Atom, hydroxy, C_1-4Alkoxy or nitro group or co-
To form a condensed aromatic ring,   R⁹Is a hydrogen atom, C_1-4An alkyl or aryl group,   X is an oxygen or sulfur atom, group> NR¹²Or -CH = CH-,
R here¹²Is C_1-4Alkyl, C_2-4Carboxyalkyl, C_2-4Sulfo
Alkyl, C_2-4Sulfoxyalkyl, C_2-4Hydroxyalkyl or
Is a ralkyi group,   Y⁻Halide, C_1-4Alkyl sulphate, C_1-4Alkane sulfone
Lute, arene sulfonate, C_1-4Perfluoroalkane sulfonate, te
Trafluoroborate, perhalogenate, sulphate, hydrogen sulphate
Or an anion selected from carbonates. ];   Formula III: [Chemical 3] [In the formula,   R¹⁰Is C_1-4Acyl group, aroyl, C_1-4Alkylsulfonyl, C_{1- Four} Alkylsulfinyl, C_1-4Alkylamino, di-C_1-4-Alkyla
Mino, vinyl carbonyl, methine imino, nitrile, ester or carboxylic acid
Amido group (optionally C_1-4Alkyl, C_2-4Hydroxyalkyl or
Optionally substituted with an aryl group),   R¹¹Is C_1-4Acyl, C_1-4Alkoxy, C_1-4Alkylamino, C _1-4 Acylamino or di-C_1-4An alkylamino group,   Substituent R¹⁰And R¹¹In cooperation with the rest of the molecule, 1,3-thiazolidine
-2,5-diones, 1,3-thiazolidine-2-thione-5-ones, perch
Doropyrimidine-2,4,6-triones, perhydropyrimidine-2-thione
-4,6-diones, cyclopentane-1,3-diones, cyclohexane-1
, 3-diones, indoles, indane-1,3-diones, indane-1-
Ones, 2-pyrazolin-5-ones, 1,2-dihydro-6-hydroxy-2
Selected from the series of hydroxypyridines or their enol esters
Forming a 5-, 6- or 7-membered heterocycle,   Z is an oxygen, sulfur or dicyanomethylene group. ]. 2. As the compound represented by the formula I, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 4-piperidino Benzaldehyde, 4-dimethylaminoacetophenone, 4-dimethylaminonaphthalaldehyde, 4-dimethylaminobenzylideneacetone, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino- 2-methylbenzaldehyde, trans-4-diethylaminocinnamaldehyde, 4- (dibutylamino) -benzaldehyde, 4-diphenylaminobenzaldehyde, 2,3,6,7-Tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 2,3,6,7-tetrahydro-8-hydroxy- 1H
, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 4- (1-imidazolyl) -benzaldehyde, 2-morpholinobenzaldehyde, indole-3-carboxaldehyde, 1-methylindole-3-carboxaldehyde,
N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3
-The composition according to claim 1, wherein trimethylindoline (Fischer aldehyde or tribasic aldehyde) and mixtures thereof are used. 3. As the compound represented by the formula II, 1,4-dimethylquinolinium, 1,2-dimethylquinolinium, 1,4-dimethylpyridinium, 1,2-
Dimethylpyridinium, 2-methyl-1-ethylquinolinium, 2,3-dimethylisoquinolinium, 1,2,3,3-tetramethyl-3H-indolinium,
2,3-Dimethylbenzothiazolium, 2,3-dimethyl-6-nitrobenzothiazolium, 3-benzyl-2-benzothiazolium, 2-methyl-3-propylbenzothiazolium, 2,4 -Dimethyl-3-ethylthiazolium, 3- (2
-Carboxyethyl) -2,5-dimethylbenzothiazolium, 1,2,3-trimethylbenzimidazolium, 5,6-dichloro-1,3-diethyl-2-methylbenzimidazolium, 3-ethyl-2 -Methylbenzothiazolium, 3-
Ethyl-2-methylnaphthol [1,2-d] thiazolium, 5-chloro-3-
Ethyl-2-methylbenzothiazolium, 3-ethyl-2-methylbenzoxazolium salt (for example, chloride, bromide, iodide, methanesulfonate, benzenesulfonate, p-toluenesulfonate, trifluoromethanesulfonate, methylsulfate) , Tetrafluoroborate), and 2-methyl-3- (3-sulfopropyl) -benzothiazolium hydroxide, inner salt, 5-methoxy-2-methyl-3- (3-sulfopropyl). ) -Benzothiazolium hydroxide, inner salts, and mixtures thereof are used. 4. Rhodanine, Rhodanine-as the compound of formula III
3-acetic acid, barbituric acid, thiobarbituric acid, 1,3-dimethyl and 1,
3-diethylthiobarbituric acid, oxindole, 3-indoxyl acetate, coumaranone, 1-methyl-3-phenylpyrazolinone, indane-1,3-
Dione, cyclopentane-1,3-dione, 1,2-dihydro-1-ethyl-6
A composition according to any one of claims 1 to 3 which uses -hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile and mixtures thereof. 5. The reaction product of the compounds of formula I and formula II and / or formula III is Quinaldine Red (2- [4- (dimethylamino) -styryl] -1-ethylquinolinium iodide). , 2- [4- (dimethylamino) -styryl]-
1-methylquinolinium iodide, 2- [4- (dimethylamino) -styryl] -1-ethylpyridinium iodide, 2- [4- (dimethylamino) -styryl] -1-methylpyridinium iodide, 4 -[4-Dimethylaminostyryl] -1-methylpyridinium tosylate, 4- [2- (2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolidin-9-yl) -ethenyl]-
1-methylpyridinium iodide, trans-4- [4- (dibutylamino)
-Styryl] -1-methylpyridinium iodide and 2,6-bis- [4-
(Dimethylamino) -styryl] -1-methylpyridinium iodide, 2- [
4- (dimethylamino) -styryl] -3-methylbenzoxazolium perchlorate, 2- [4- (dimethylamino) -styryl] -3-methylbenzoxazolium iodide, 2- [4- (dimethyl) A composition according to any of claims 1 to 4 selected from amino) -styryl-1-ethylnaphthol [1,2-d] thiazolium iodide and mixtures thereof. 6. An aromatic aldehyde or ketone of formula I, and formula II
A quaternary heterocyclic compound represented by: and a CH-active compound represented by formula III:
6. The composition according to claim 1, which is used in an amount of 0.03 to 65 mmol, especially 1 to 40 mmol, per 100 g of the total dye composition. 7. Piperidine, piperidine-2-carboxylic acid, piperidine-3
-Carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, imidazole, 1-methylimidazole, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, 7. A composition according to any one of claims 1 to 6 containing a color improver selected from the group consisting of pyrazole, 1,2,4-triazole, piperazine or mixtures thereof. 8. Nitrophenylenediamines, nitroaminophenols,
A composition according to any one of claims 1 to 7 which contains a direct dye selected from the group consisting of anthraquinones or indophenols, preferably in an amount of 0.01 to 20% by weight, based on the total dye composition. . 9. Alkali metal (eg potassium, sodium or lithium), alkaline earth metal (eg magnesium, calcium, strontium or barium) or aluminum, manganese, iron, cobalt, copper or zinc formate, carbonate. , Halide, sulphate, butyrate, valerate, capronate, acetate, lactate, glycolate, tartrate, citrate, gluconate, propionate, phosphate and phosphonate The composition according to claim 1, further comprising a metal salt or an ammonium salt selected from the group consisting of: 10. Oxidizing agent, in particular H ₂ O ₂ , of 0.0 to the applied solution.
The composition according to any one of claims 1 to 9, which is contained in an amount of 1 to 6% by weight. 11. The composition according to claim 1, which contains an anionic, zwitterionic or nonionic surfactant. 12. An aromatic aldehyde or ketone of formula I and a compound of formula II
And / or a combination with a CH-active compound of formula III, and / or
Is the use of the reaction product of the above compound as a dyeing component in an oxidative hair dyeing composition:   Formula I: [Chemical 4] [In the formula, R¹Is a hydrogen atom, C_1-4An alkyl group or an aryl group,   R^TwoAnd R^ThreeAre independently of each other a hydrogen atom, C_1-4Alkyl group, halogen source
Child, hydroxy, C_1-4An alkoxy or nitro group or jointly
Forming a condensed aromatic ring,   R^FourAnd R⁵Is a hydrogen atom, C_1-4Alkyl, C_2-4Hydroxy alk
Le, C_1-4An alkenyl or aryl group, or in combination with a nitrogen atom
, A 5- to 7-membered heterocycle, or one of them is a substituent R^TwoOr R^Three Forming a saturated or unsaturated 5-, 6- or 7-membered ring with one of   Q is a direct bond or a vinylene or vinylidene group, which has two substitutions
Group R^FourOr R⁵Forms an indole ring or (an exocyclic double bond with one of the
In some cases) may form an indoline ring,   n is 1 or 2. ];   Formula II: [Chemical 5] [In the formula,   R⁶Is C_1-10Alkyl, C_2-10Alkenyl, C_2-4Hydroxyal
Kill, C_2-4Carboxyalkyl, C_2-4Sulfoalkyl or aralkyl
The base,   R⁷And R⁸Are independently of each other a hydrogen atom, C_1-4Alkyl group, halogen
Atom, hydroxy, C_1-4Alkoxy or nitro group or co-
To form a condensed aromatic ring,   R⁹Is a hydrogen atom, C_1-4An alkyl or aryl group,   X is an oxygen or sulfur atom, group> NR¹²Or -CH = CH-,
R here¹²Is C_1-4Alkyl, C_2-4Carboxyalkyl, C_2-4Sulfo
Alkyl, C_2-4Sulfoxyalkyl, C_2-4Hydroxyalkyl or
Is a ralkyi group,   Y⁻Halide, C_1-4Alkyl sulphate, C_1-4Alkane sulfone
Lute, arene sulfonate, C_1-4Perfluoroalkane sulfonate, te
Trafluoroborate, perhalogenate, sulphate, hydrogen sulphate
Or an anion selected from carbonates. ];   Formula III: [Chemical 6] [In the formula,   R¹⁰Is C_1-4Acyl group, aroyl, C_1-4Alkylsulfonyl, C_{1- Four} Alkylsulfinyl, C_1-4Alkylamino, di-C_1-4-Alkyla
Mino, vinyl carbonyl, methine imino, nitrile, ester or carboxylic acid
Amido group (optionally C_1-4Alkyl, C_2-4Hydroxyalkyl or
Optionally substituted with an aryl group),   R¹¹Is C_1-4Acyl, C_1-4Alkoxy, C_1-4Alkylamino, C _1-4 Acylamino or di-C_1-4An alkylamino group,   Substituent R¹⁰And R¹¹In cooperation with the rest of the molecule, 1,3-thiazolidine
-2,5-diones, 1,3-thiazolidine-2-thione-5-ones, perch
Doropyrimidine-2,4,6-triones, perhydropyrimidine-2-thione
-4,6-diones, cyclopentane-1,3-diones, cyclohexane-1
, 3-diones, indolines, indane-1,3-diones, indane-1-
Ones, 2-pyrazolin-5-ones, 1,2-dihydro-6-hydroxy-2
Selected from the series of hydroxypyridines or their enol esters
Forming a 5-, 6- or 7-membered heterocycle,   Z is an oxygen, sulfur or dicyanomethylene group. ]. 13. A method for dyeing keratin-containing fibers (especially human hair).
An aromatic aldehyde or ketone of formula I and a formula II and / or formula III
With a CH-active compound represented by and / or reaction of the above compound
The product, as well as the dye composition containing the usual cosmetic ingredients, is suitable for keratin-containing fibers.
And leave it for a while (usually about 30 minutes) before rinsing off or shampooing.
A method comprising washing off with a pump.   Formula I: [Chemical 7] [In the formula, R¹Is a hydrogen atom, C_1-4An alkyl group or an aryl group,   R^TwoAnd R^ThreeAre independently of each other a hydrogen atom, C_1-4Alkyl group, halogen source
Child, hydroxy, C_1-4An alkoxy or nitro group or jointly
Forming a condensed aromatic ring,   R^FourAnd R⁵Is a hydrogen atom, C_1-4Alkyl, C_2-4Hydroxy alk
Le, C_1-4An alkenyl or aryl group, or in combination with a nitrogen atom
, A 5- to 7-membered heterocycle, or one of them is a substituent R^TwoOr R^Three Forming a saturated or unsaturated 5-, 6- or 7-membered ring with one of   Q is a direct bond or a vinylene or vinylidene group, which has two substitutions
Group R^FourOr R⁵Forms an indole ring or (an exocyclic double bond with one of the
In some cases) may form an indoline ring,   n is 1 or 2. ];   Formula II: [Chemical 8] [In the formula,   R⁶Is C_1-10Alkyl, C_2-10Alkenyl, C_2-4Hydroxyal
Kill, C_2-4Carboxyalkyl, C_2-4Sulfoalkyl or aralkyl
The base,   R⁷And R⁸Are independently of each other a hydrogen atom, C_1-4Alkyl group, halogen
Atom, hydroxy, C_1-4Alkoxy or nitro group or co-
To form a condensed aromatic ring,   R⁹Is a hydrogen atom, C_1-4An alkyl or aryl group,   X is an oxygen or sulfur atom, group> NR¹²Or -CH = CH-,
R here¹²Is C_1-4Alkyl, C_2-4Carboxyalkyl, C_2-4Sulfo
Alkyl, C_2-4Sulfoxyalkyl, C_2-4Hydroxyalkyl or
Is a ralkyi group,   Y⁻Halide, C_1-4Alkyl sulphate, C_1-4Alkane sulfone
Lute, arene sulfonate, C_1-4Perfluoroalkane sulfonate, te
Trafluoroborate, perhalogenate, sulphate, hydrogen sulphate
Or an anion selected from carbonates. ];   Formula III: [Chemical 9] [In the formula,   R¹⁰Is C_1-4Acyl group, aroyl, C_1-4Alkylsulfonyl, C_{1- Four} Alkylsulfinyl, C_1-4Alkylamino, di-C_1-4-Alkyla
Mino, vinyl carbonyl, methine imino, nitrile, ester or carboxylic acid
Amido group (optionally C_1-4Alkyl, C_2-4Hydroxyalkyl or
Optionally substituted with an aryl group),   R¹¹Is C_1-4Acyl, C_1-4Alkoxy, C_1-4Alkylamino, C _1-4 Acylamino or di-C_1-4An alkylamino group,   Substituent R¹⁰And R¹¹In cooperation with the rest of the molecule, 1,3-thiazolidine
-2,5-diones, 1,3-thiazolidine-2-thione-5-ones, perch
Doropyrimidine-2,4,6-triones, perhydropyrimidine-2-thione
-4,6-diones, cyclopentane-1,3-diones, cyclohexane-1
, 3-diones, indolines, indane-1,3-diones, indane-1-
Ones, 2-pyrazolin-5-ones, 1,2-dihydro-6-hydroxy-2
Selected from the series of hydroxypyridines or their enol esters
Forming a 5-, 6- or 7-membered heterocycle,   Z is an oxygen, sulfur or dicyanomethylene group. ].